Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers

Definitions

• This invention relates to the preparation of pulverulent polymers and copolymers of vinyl chloride.
• a method of preparing pulverulent polymer or copolymer compositions based on vinyl chloride and suitable for immediate use in which there is prepared a master mixture by mixing, in an aqueous medium, one or more polymers and/or copolymers based on vinyl chloride and the various additives necessary for their use including, liquid additives and fusible solid additives, the liquid additives and at least a part of the fusible solid additives being introduced with agitation into the mixing zone in the form of one or more dispersions of finely divided particles of a homogeneous phase in water, and the master mixture thus obtained is thereafter mixed with polymers and/or copolymers based on vinyl chloride.
• the proportion of polymers and/or the copolymers based on vinyl chloride used for the preparation of master mixture may be from 40 to 90% and preferably from 60 to 80% by weight of the master mixture.
• a pulverulent composition suitable for immediate use.
• the amount of master mixture used in the preparation of such a composition should be at least 10% and preferably between 20 and 60% by weight of the final composition.
• the polymers and copolymers based on vinyl chloride used for the preparation of the master mixture may be prepared by any known process: bulk polymerization, suspension polymerization, polymerization in fine suspension or emulsion polymerization. The same applies to polymers and copolymers based on vinyl chloride intended to be mixed with master mixtures to obtain compositions suitable for immediate use.
• the master mixture may contain polymer modifying agents such as polymethyl methacrylates; graft polymers and copolymers such as styrene and acrylonitrile on polybutadiene or styrene-butadiene copolymer, styrene and methyl methacrylates or polybutadiene or styrene-butadiene copolymer, butadiene and acrylonitrile on vinyl chloride polymer or copolymer, vinyl chloride on ethylene-vinyl acetate copolymer; copolymers of olefins and vinyl monomers such as copolymers of ethylene and vinyl acetate.
• the quantity of polymer modifying agent may range from 0 to 30 parts by weight per 100 parts by weight of polymers and copolymers based on vinyl chloride.
• the liquid additives may be pure liquid ingredients or solutions of solid ingredients in appropriate solvents, such as plasticizers. Included in this category are stabilizers for polymers and copolymers based on vinyl chloride, such as organic tin salts, short chain metallic soaps; lubricants such as esters of glycerol and oleic acid, esters of glycerol and ricinoleic acid; antioxidants such as trinonylphenylphosphite; plasticizers such as dioctyl phthalate and epoxidized soya oil.
• the quantity of plasticizer used may range from 0 to 10 parts by weight per 100 parts by weight of polymer and copolymer based on vinyl chloride.
• the solid fusible additives may be lubricants, such as wax esters, natural waxes, polyethylene waxes, paraffin waxes, fatty acids, fatty alcohols, amines of fatty acids and stabilizers, such as alphaphenylindole and calcium hydroxystearate.
• lubricants such as wax esters, natural waxes, polyethylene waxes, paraffin waxes, fatty acids, fatty alcohols, amines of fatty acids and stabilizers, such as alphaphenylindole and calcium hydroxystearate.
• Each of the liquid additives and the solid fusible additives may be introduced separately into the mixing zone in which the master mixture is made, such as in the form of a finely divided aqueous dispersion of a homogeneous phase. It is however generally preferable to make the introduction with a minimum number of aqueous dispersions, using a minimum number of homogeneous phases; this minimum number is a function of the reciprocal miscibility of said additives.
• the homogeneous phase may be formed by heating the additives at temperatures generally between 20° and 150° C.
• a dispersing agent which is chemically inert with respect to the additives to be dispersed, under strong agitation, at a temperature from 20° to 100° C., and then to pass this predispersion through a homogenizer, such as an ultrasonic or turbine homogenizer.
• emulsifying agents which are non-ionic, such as alkylphenolpolyoxyethylenes, protective colloids such as methylcelluloses, polyvinyl alcohol, and the copolymers of maleic anhydride and styrene partially neutralized with potassium or sodium hydroxide. They may generally be used in an amount of 0.2 to 20% by weight with respect to the homogeneous phase to be dispersed.
• the concentration of the homogeneous phase in the aqueous dispersion may normally be from 10 to 40% by weight.
• the droplets of the homogeneous phase in the dispersion preferably have a mean diameter from 1 to 30 microns and most preferably between 10 and 20 microns. It may be advantageous continuously to prepare the aqueous dispersion of the homogeneous phase immediately before use to limit hydrolysis at high temperature, especially when hydrolyzable additives are present.
• solid ingredients which are usable directly in the form of an aqueous dispersion such as for example the polymers and copolymers based on vinyl chloride and polymer modifying agents prepared in aqueous medium, are advantageously introduced in this form to the mixing zone.
• the solid ingredients which cannot be made into a homogeneous phase and which therefore are not directly usable in the form of an aqueous dispersion, may be added into the mixing zone either in the form of a concentrated pulverulent composition or as such possibly after wetting by means of an aqueous solution of a wetting agent.
• a concentrated composition of these ingredients in the form of particles having an average grain size close to that of the master mixture to be prepared may be obtained by dry mixing under agitation at high speed and at a temperature generally from 50° to 130° C., in an amount 5 to 20 times their weight of the polymer or copolymer based on vinyl chloride.
• This category of additives includes lubricants, such as certain polyethylene waxes which, not being miscible with any of the liquid additives or other solid fusible additives and having a very high viscosity in the molten state, are difficult to bring into the form of a finely divided aqueous dispersion of a homogeneous phase.
• lubricants such as certain polyethylene waxes which, not being miscible with any of the liquid additives or other solid fusible additives and having a very high viscosity in the molten state, are difficult to bring into the form of a finely divided aqueous dispersion of a homogeneous phase.
• ingredients in the form of very fine particles of diameter generally less than 4 microns, such as colorants, because they become firmly fixed to particles of polymers and copolymers and cannot be accidentally eliminated during later treatment.
• the addition of all the ingredients to the mixing zone, maintained under agitation may be carried out by simultaneous or successive introductions in any order.
• the polymers and copolymers used are introduced partly in the form of a latex certain precautions should be taken regarding the time of introduction of the latex depending on whether the latter are composed of polymers or copolymers which are sticking or non-sticking.
• the introduction in the mixing zone of a latex of sticking polymers or copolymers, hereinafter identified by the letter A, may be carried out before, during, or after the operation of mixing in the other ingredients but preferably before.
• the introduction of the latex of polymers or copolymers which are non-sticking hereinafter identified by the letter B, should be carried out after the mixing operation for the other ingredients is finished, otherwise the composition will not be homogeneous.
• the polymers or copolymers which are non-sticking are defined as polymers or copolymers which do not tend to agglomerate.
• non-sticking polymer there is understood any polymer or copolymer of which the temperature of second order transition (vitreous transition Tg, according to R. F. Bayer, R. S. Spencer-Advances in Colloids Science 2-Interscience) is greater than 0° C., and preferably greater than 30° C. and of which the modulus of elasticity in stretching (Standard ASTM.D638-61T) is greater than 1000 kg/cm2 and preferably greater than 10000 kg/cm2.
• non-sticking polymers and copolymers there may be mentioned polyvinyl chloride; polymethylmethacrylates; graft polymers and copolymers such as styrene and acrylonitrile on polybutadiene or styrene-butadiene copolymer, styrene and methylmethacrylate on polybutadiene or styrene-butadiene copolymer, vinyl chloride on ethylene-vinyl acetate copolymer; copolymers of olefins and vinyl monomers such as copolymers of ethylene and vinyl acetate.
• sticking polymers there may be mentioned the polymers obtained by grafting, in emulsion, of a diene monomer possibly added to at least one vinyl monomer on a polymer or copolymer chain of vinyl chloride. This is the case, for example, with polymers obtained by grafting butadiene and acrylonitrile on polyvinyl chloride.
• the operation of mixing may be carried out in a vessel, which may be an autoclave, which has been used for preparation of one of the polymers or copolymers intended for the preparation of the composition according to the invention.
• the concentration of dry matter in the aqueous medium is adjusted, if necessary, by addition of water and is generally between 20 and 40% and preferably 25 to 35% by weight.
• the temperature of the aqueous medium may be maintained between 20° and 90° C. and preferably from 25° to 60° C., possibly by heating by means, for example, of injection of steam. In this case there is advantage in proceeding with the operation of mixing under agitation at high turbulence.
• the end of the mixing operation may be detected by removing and optically examining, with a microscope, an aliquot of aqueous composition. This examination shows that when the operation is finished the particles obtained are formed of particles of polymer and copolymer prepared by polymerization in aqueous suspension or in bulk, on which are fixed the other particles with the exception however of a part of the particles forming the latex A which may be used.
• the duration of the operation of mixing is in this case greater as the concentration of the aqueous medium in dry matter is lower, the agitation less violent and the temperature lower. By way of indication, this duration may vary from 2 minutes to 2 hours, depending on the operating conditions.
• the aqueous composition may then be subjected to heat treatment which consists of heating and agitating at a temperature from 60° to 100° C., such as by injection of steam, for a period of 2 to 60 minutes.
• the duration of this treatment may advantageously be reduced by operating continuously to limit possible hydrolysis.
• This thermal treatment which facilitates the final elimination of the aqueous phase, also has the effect of causing the additives to penetrate to the inside of the particles of polymer and copolymer on which they are fixed and thus to perfect the mixing which becomes evident after separation of the liquid medium, as for example, by vacuum filtration and drying, to provide a homogeneous pulverulent composition which flows freely and which is usable as a master mixture.
• the composition obtained may have the appearance of mud possessing poor flow properties.
• the concentration in the aqueous medium of dry matter, after introduction of the ingredients in the mixing zone is generally from 15 to 45% by weight.
• the operation of mixing is practically instantaneous and completed at the end of introduction of the ingredients to the mixing zone. At this stage, all the particles used are intimately mixed but retain their individuality.
• aqueous composition it is possible, however, to submit the aqueous composition to an operation of atomization, generally between 55° and 110° C., after possible dilution, to coagulate the latex by addition of a solution of a coagulating agent, submit the aqueous composition to a heat treatment identical to that described in the case where at least a part of the polymers or copolymers used have been prepared by polymerization in aqueous suspension or in bulk, separate the composition of the liquid medium for example by vacuum filtration, followed by drying. There is then obtained a pulverulent homogeneous free-flowing composition usable as a master mixture.
• coagulation agents such as calcium chloride
• They are generally used in the quantity of 0.2 to 5% by weight with respect to the polymers and copolymers forming the latex to be coagulated.
• the master mixture and the polymers and/or copolymers based on vinyl chloride may be mixed in a dry state by fluidization or mechanically, for example by means of a mixer operating at slow speed or continuously by means of a dosing device which may be connected to a fabrication machine.
• the master mixture and said polymers and/or copolymers may be mixed in aqueous medium in the form of their respective aqueous suspensions. In this case, that is either the master mixture on its own in the form of its aqueous suspension, or the final aqueous composition, may be subjected to the thermal treatment described above.
• the pulverulent compositions of polymers and copolymers based on vinyl chloride are suitable for manufacture of rigid articles by molding, calendering, injection, extrusion, extrusion-blowing and especially for manufacture by extrusion blowing or hollow bodies, such as bottles suitable for containing food products, such as wine and mineral waters.
• Examples 1 to 10 there is used as vinyl chloride polymer for preparation of master mixtures, a polymer S prepared by polymerization in aqueous suspension. It is introduced into the mixing zone in the form of the aqueous suspension in which it is made containing 31% by weight polymer.
• plastic compositions suitable for immediate use are prepared by mixing in aqueous medium, in the form of their respective aqueous suspensions, of the master mixture and the polymer S.
• compositions suitable for immediate use are prepared by mixing in the dry state the master mixture and polymer S or a polymer M prepared by bulk polymerization.
• Example 11 there is used, as polymer of vinyl chloride, for preparation of the master mixture, a polymer E prepared by polymerization in aqueous emulsion. It is introduced into the mixing zone in the form of the latex in which it was obtained containing 31% by weight of dry material.
• Example 11 the composition suitable for immediate use is prepared by mixing in the dry state of the master mixture and polymer E obtained by atomization of its latex.
• the polymers S, M, and E are polyvinyl chlorides having an AFNOR viscosity index of 80, determined according to Standard NFT 51013.
• the master mixture is transferred during 5 hours into a vessel of 100 M 3 capacity, provided with two superposed turbines having four inclined blades turning at 40 revs. per minute and containing 54 tons of the aqueous suspension of polymer S, previously cooled to 40° C. by means of an intermediate vessel of 5 M 3 capacity, in which it is heated to 90° C. by injection of steam.
• the dwell time in this vessel is 30 minutes and the final temperature of the mixture obtained in the vessel of 100 M 3 capacity is stabilized at about 60° C.
• the pulverulent composition obtained has a granulometric distribution close to that of polymer S.
• the operations of filtering and drying of the aqueous composition may be carried out in conventional industrial plant used for recovery of polymers of vinyl chloride prepared by polymerization in aqueous suspension.
• composition obtained is capable of being subjected, without further treatment, to subsequent fabricating operations such as molding, calendering, extrusion, blow molding, and injection, to give rigid shock resistant articles which are transparent and of color which is very slightly yellow.
• Example 1 The procedure of Example 1 is followed but the master mixture contained in the vessel of 50 M 3 capacity is treated continuously for 5 hours by passage through two vessels of 5 M 3 capacity in series, the first in which the master mixture is heated to 90° C. by injection of water vapor, the second provided with a jacket in which it is cooled to 60° C. by circulation of water in the jacket.
• the master mixture, thus treated, is filtered and dried.
• the master mixture, thus obtained, is recovered in a silo in which it is mixed by fluidization with 16.74 tons of polymer S or polymer M.
• Example 2 The procedure of Example 2 is followed except that, after drying, the master mixture is mixed continuously with 16.74 tons of polymer S or polymer M by means of a screw operated metering device which is connected to feed a fabricating machine.
• the articles obtained have the same properties as those obtained from compositions prepared as in Examples 1 and 2.
• Example 2 The procedure of Example 2 is followed except that, after drying of the master mixture, there is mixed 132 kg of master mixture with 167 kg of polymer S or polymer M in a mixer at slow speed having a useful capacity of 600 liters. The duration of mixing is 30 minutes.
• the master mixture thus obtained, is transferred in 5 hours into a vessel of 100 M 3 capacity used in Example 1, in which the turbines rotate at 40 turns per minute, and containing 67.5 tons of the aqueous suspension of polymer S, previously cooled to 50° C., by means of an intermediate vessel of 3 M 3 capacity in which it is heated at 90° C. by injection of steam.
• the dwell time in this intermediate vessel is 30 minutes and the final temperature of the mixture obtained in the vessel of 100 M 3 capacity is stabilized at about 60° C.
• an aqueous dispersion of a homogeneous phase prepared in the following manner: in a melting device at 100° C., there is made by heating of the ingredients, a homogeneous phase composed of 1000 kg of dioctyl tin bis-isooctyl-mercaptoacetate, 250 kg of oxidized polyethylene wax, 200 kg of glycerol trihydroxystearate and 25 kg of a blue colorant. Said homogeneous phase is fed under violent agitation, obtained by means of a turbine of 200 mm diameter turning at 3000 turns per minute, into 4 tons of an aqueous solution having 2% by weight of sodium dioctylsulpho-succinate, said solution previously being brought to 80° C.
• the master mixture thus obtained, is treated continuously for 5 hours by passage through two vessels of 5 M 3 capacity in series, the first in which the master mixture is heated to 90° C. by injection of steam, the second, provided with a jacket, in which it is cooled to 60° C. by circulation of water in the jacket.
• the master mixture thus treated is filtered and dried.
• the master mixture thus obtained is fed to a silo in which it is mixed by fluidization with 60 tons of polymer S or polymer M.
• the master mixture thus obtained, is treated continuously for 5 hours by passage through two vessels of 5 M 3 capacity in series, the first in which the master mixture is heated to 90° C. by injection of steam, the second, provided with a jacket, in which it is cooled to 60° C. by circulation of water in the jacket.
• the master mixture thus treated is filtered and dried.
• the master mixture is collected in a silo in which it is mixed by fluidization with 63.1 tons of polymer S or polymer M.
• an aqueous dispersion of a homogeneous phase prepared in the following manner: in a vessel for melting at 110° C., there is made by heating of the ingredients, a homogeneous phase composed of 675 kg of epoxidized soya oil, 27.5 kg of zinc stearate, 40 kg of calcium stearate, 50 kg of alphaphenylindole and 270 kg of glycerol monostearate.
• aqueous suspension polymer S To the master mixture, thus obtained, there is added 4.5 tons of the aqueous suspension polymer S.
• the aqueous composition thus obtained is then treated continuously for 5 hours by passage in two vessels of 5 M 3 capacity in series, the first in which the composition is heated to 90° C. by injection of steam, the second, provided with a jacket, in which it is cooled to 60° C. by circulation of water in the jacket.
• the composition thus treated is filtered and dried.
• an aqueous dispersion of a homogeneous phase prepared in the following manner: in a melting vessel at 110° C. there is made by heating of the ingredients to form a homogeneous phase composed of 1500 kg of epoxidized soya oil, 75 kg of zinc stearate, 75 kg of calcium stearate, 100 kg of alph aphenylindole, 250 kg of glycerol monostearate and 50 kg of green coloring.
• Said homogeneous phase is fed under violent agitation, obtained by means of a turbine of 200 mm diameter turning at 3000 turns per minute, in 5 tons of an aqueous solution of 0.25% by weight copolymer of maleic anhydride and styrene partially neutralized by potassium hydroxide, said solution being previously brought to 85° C.
• the master mixture thus obtained is treated continuously for 5 hours by passage through two vessels of 2.5 M 3 capacity in series, the first in which the master mixture is heated to 90° C. by injection of steam, the second, provided with a jacket, in which it is cooled to 60° C. by circulation of water in the jacket. Ths master mixture thus treated is filtered and dried.
• the master mixture thus obtained is collected in a silo in which it is mixed by fluidization with 48 tons of polymer S or polymer M.
• Example 1 An aqueous dispersion of a homogeneous phase prepared as in Example 1.
• aqueous composition is then subjected to atomization at 90° C.

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• Organic Chemistry (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
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• 1975
  • 1975-12-11 FR FR7537921A patent/FR2334706A2/fr active Granted
• 1976
  • 1976-12-08 US US05/748,517 patent/US4119601A/en not_active Expired - Lifetime
  • 1976-12-09 ES ES454077A patent/ES454077A2/es not_active Expired
  • 1976-12-09 BE BE173116A patent/BE849239R/xx not_active IP Right Cessation
  • 1976-12-09 DE DE2655888A patent/DE2655888C2/de not_active Expired
  • 1976-12-09 AR AR265782A patent/AR213106A1/es active
  • 1976-12-10 IT IT52556/76A patent/IT1073949B/it active
  • 1976-12-10 JP JP14791976A patent/JPS5290549A/ja active Granted
  • 1976-12-10 GB GB51675/76A patent/GB1552157A/en not_active Expired
  • 1976-12-10 NL NL7613776A patent/NL7613776A/xx unknown

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